Tertiary-octylated biphenyls



comprising the same.

Patented Nov. 11, 1952 UNlTED STATES Ar NT OFFICE 2,617,837 'rEaTIAaY-ooriz'in'rrip BIPHENYLS Gerald H. Coleman, Freeland, and Raymond H. Rigterink, Midland, Mich.-, assignorsto The Dow Chemical Company, Midland, Mich, a corporation of Delaware NoDraWing. Application September 30, 1950,

Serial No, 187,836

9 Claims. (01; 260 -668) This invention concerns certain new biphenyl derivatives and a method of making the same. The biphenyl derivatives provided by the invention are tertiary-octylated biphenyls having from one to threetertiary-octyl radicals, i. e. l,1',3,3 tetramethylbutyl radicals, as the only substituentson the biphenyl nuclei, and mixtures They have the general formula i (In-n on; I redeem-(I I- CH3 CH3 n wherein n and nare integers having individual values of from to 2 and. having a sum of from 1 to 3.. In most instances, the products are initially obtained as a liqud mixture of isomeric and homologous tertiary-octylated biphenyls. The homologous compounds may be separated from one another by fractional distillation, e. g. toobtain a liquid fraction of isomeric monotertiary-octylebiphenyls,' a higher boiling liquid fraction of isomeric di- (tertiary-octyl) biphenyls, and a still higher boiling liquid fraction of tri- '(tertiary-octyl) biphenyls, etc. In some instances individual tertiary-octylated biphenyls may be isolated, e. g. by careful fractional distillation, or by fractional crystallization, etc. However, the products comprising a liquid mixture of isomeric mono-, di-, or tri-tertiaryoctylated biphenyls, or of isomers of all three such compounds together, as the principal ingredients are well suited for use as plasticizers for thermoplastic resins and are usually employed as such.

The tertiary-octylated biphenyls provided by the invention are particularly adapted for use as plasticizers for cellulose ether molding compositions. especially the ethyland higher alkyl-ethers of- It is important that the cellulose ethers,

cellulose, be plasticized prior tomolding, since number and variety of plasticizers known which may be incorporated with ethyl cellulose to permit ready and accurate molding, but nearly all of them, when used in amount sufficientfor the purpose, soften the ethyl cellulose to an extent such that the molded articles are easily scratched or marred. Also, most of the known plasticizers, when used in, amount permitting ready molding, seriously reduce the tensile strength, or impair othermechanical properties of ethyl cellulose.

Themono di and tri-tertiary octylatcd biphenyls of the invention are highly effective as plasticizers for ethyl cellulose and do not cause excessive softening of the latter at room temperature. They can be incorporated with ethyl cellulose, or other alkyl ethers of cellulose, to ob- ,tain compositions which may be molded readily the impact strength and the per cent elongation value, etc. l

The tcrtiary-octylated biphenyls are made by reacting diisobutylene with biphenyl in the presence of. a Friedel-Crafts catalyst, e. g. aluminum chloride, aluminum bromide, or. .boron trifluoride, etc. Aluminum chloride is usually employed as the catalyst in amount corresponding to from .2 to 5 per cent of the weight of the biphenyl, but it may be used in smaller or larger proportions. From one to two molecular equivalents of diisobutylene are preferably employed per mole of hiphenyl, but smaller-or much larger proportions, e. g. from 0.5 to e molecular equivalents, or diisobutylene can be used. The reaction is carried out at temperatures such as to 'liquefy the reaction mixture and not higher than 100 C. At higher temperatures, the diisobutylene, or the tertiary octyl radicals, tend to undergo decominto the products. The reaction is usually conducted at temperatures between and C.,

preferably between 70 and 90 C., but lower tem-' peratures can be used, e. g. after the reaction is started.

In practice, the biphenyl is melted, the cat- 4 EXAMPLE 2 Approximately two molecular equivalents of diisobutylene and one mole of biphenyl were alyst added, and the diisobutylene is gradually 5; reacted together in the presence of aluminum introduced While stirring and warming the chloride and the mixture was washed with wature' when conducted at temperaturgs between ter and fractionally distilled, as in Example 1. and 800 using aluminum chlonde the The results were similar to those obtained in catalyst, the reaction is usually complete 1n less Example 1 except that approximately equal than 4 hours. The mixture is then cooled and 1 Weights of monmtertiarymctylated biphenyl the catalyst is destroyed or a by and di-tertiary-octylated biphenyl were obtained treatment with alkali or by washmg mth y as the principal products, tritertiary-octylated an aqueous alkali solution, or an aqueous acid biphenyl being obtained in minor amount solution, etc. When employing thle7 reactants2 the preferred proportions herein e ore s a e the product consists for the most part of mono- EXAMPLE 3 and di-tertiary-octylated biphenyls, but contains a m nor a unt of tri-teltiary-octylated b p The three tertiary-octylated biphenyl products 311 together w h unreacted biphenyl diisoobtained in Example 1 were separately tested blltylene- It y be dried and employeddil'ectly as plasticizers for ethyl cellulose. In each exas a plasticizer, but is preferably first distilled periment, one part by weight of the tertiaryto remove unreacted Starting materials d t0 octylated biphenyl and four parts of ethyl cellu- Separate t11191110110, and tri'tertiary'octylated lose were admixed and the mixture was warmed biphenyls from one another from any higher preparatory to milling the same on heated combomng bypmductspounding rolls until substantially uniform. All

The mono" and tri'tertiary'octylated of the mixtures withstood the heating and mill- Phenyl products be incorporated on ing operations without becoming decomposed or compounding Wlth ethyl Qeuulose or Pt darkened appreciably. Each of these composicellulose ethers to obtain molding compos t ons tions, after being rendered homogeneous, was of good qua.lity' Such moldmg composltlpm injection molded to form well dimensioned test usually contain from 1 5 to 30 per cent by weight bars of good appearance- The test bars were tertlary'9ctylated biphenyl but the ter may used to determine the tensile strength, the per be present m Smaller or larger proper Ions" cent elongation value, the impact strength both Although particularly adapted for use as plast C and t 180 C the heat distortion tem ticizers for cellulose ethers, the tertiary-octylated a a perature and the hardness of each molded mabiphenyl products may also be employed for other t 1 t d t th d T I d purposes, e. g. as plasticizers for other organic by 5 an ar es me O he Z0 thermoplastics Such as polymerized methy1 pact strength was measured in conventional methacrylate, or the rubbery copolymers of stymanner f P that w bar employed In rene and butadiene, etc., or as organic solvents. 40 F determmatlon had (11111611510115 0f /2 X /2 X V4 The following examples describe ways in which mches 91.161 was tranlsvelsely notched to a depth the principle of the invention has been applied of 0-015 H1011 across 1135 /4 inch edge at the midand illustrate certain of its advantages, but are p nt in the length of the bar. In the test, it not to be construed as limiting the invention. was struck on the notched edge. The heat distortion temperature was determined by the pro- EXAMPLE 1 cedure of A. S. T. M. bulletin 134 37-41 (19%) using a test bar having dimensions of 2%; x A x A v inches. The test bars used in determining the a g s gg g g ggfiigfig gififi i fii tensile strength and the per cent elongation value 3 2 heafed to between and C Approxi (i. e. the per cent of its original length by which mately 673 grams (6 moles) of diisobutylene was a bar be sfiretched before n were added dropwise and with stirring over a, period approxlmately 7 Inches longand of /2 Inch X /2 of 25 hours while maintainmg the mixture at inch rectangular cross section. Hardness was temperatures of from to After adding determined as Rockwell hardness on the R scale. the diisobutylene, the mixture was stirred and The f0 110W1ng table ldentlfies the a y- W maintained at from to C. for 1 hours. ated bip eny which was tested as a p asticizer It was then Washed thoroughly with water and in each experiment, by giving the distillation temiractionally distilled. The following fractions perature range of the same, Th tabl li t were collected as the principal products. 60 properties which were determined for moldings Table I ammo. Distilling Range D ip i n 273 ttftttis; lig t tiilfit il 'fifi fiitl I sityoi0.944at33C.;m=1.5559. 2 211-220 (1/3 mm. Principally (ii-tertiary octylated biphenyls; light yellow, viscous 5(igigisity of 0.932 at 33 0.; 3; 240 0.13 mm. to 255 91 Principally Stritertiary-octylated hy- O,/1 mm, phenyls; highly viscous yellow liquid; density of 0.923 at 33 0.; nn 1.6375.

of each of the plasticized ethyl cellulose compositions.

7. A mixture of isomeric tri-(1,1,3,3-tetramethylbutyl) biphenyls.

Table II Properties of Plasticized Ethyl Cellulose Moldings Distilling Range of Impact Strength as Run Plasticizer Tensile Percent inch-lbsJsampie- Heat Hub Strength Elonga- Distortion, ness lbs/sq. in. tion 'Iemp., C.

at 25 C. at l8 C.

183-191 C mm 4, 991 9. 7 3.5 1.0 56 90 211220 (.[3 mm 6, 063 9.8 3.1 0.8 62 94 240 0.]3 mm. to 255 v C./l mm 6, 127 D. 6 2.3 0.6 65 107 Other modes of applying the princi le of the invention may be employed instead of those explained, change being made as regards the products herein disclosed, provided the compound or compounds stated by any of the following claims or the equivalent of such stated compound or compounds be employed.

We therefore particularly point out and distinctly claim as our invention:

1. Tertiary-octylated biphenyl wherein every tertiary-octyl radical is the 1,1,3,3-tetramethylbutyl radical, which tertiary-octylated biphenyl contains at least 50'per cent by weight of at least one of the compounds monotertiary-octylbiphenyl and di-tertiary-octyl-biphenyl.

2. Amono-(1,1,3,3-tetramethylbutyl) biphenyl.

3. A di-(1,1,3,3-tetramethylbutyl) biphenyl.

4. Atri-(1,1,3,3-tetramethylbutyl) biphenyl.

5. A mixture of isomeric mono-(1,1,3,3-tetramethylbutyl) biphenyls.

6. A mixture oi. isomeric di-(1,1,3,3-tetramethylbutyl) biphenyls.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,172,391 Krase Sept. 12, 1939 2,491,120 Loane et a1. Dec. 13, 1949 

1. TERTIARY-OCTYLATED BIPHENYL WHEREIN EVERY TERTIARY-OCTYL RADICAL IS THE 1,1,3,3-TETRAMETHYLBUTYL RADICAL, WHICH TERTIARY-OCTYLATED BIPHENYL CONTAINS AT LEAST 50 PER CENT BY WEIGHT OF AT LEAST ONE OF THE COMPOUNDS MONOTERTIARY-OCTYLBIPHENYL AND DI-TERTIARY-OCTYL-BIPHENYL. 